Process to improve the flow of oxide during field oxidation by fluorine doping

ABSTRACT

A method of forming isolation structures in semiconductor substrates comprising exposing a region of the semiconductor simultaneously to a transforming agent and to a viscosity reducing agent so that the transforming agent transforms a portion of the substrate into an isolation structure and the viscosity reducing agent reduces the viscosity of the isolation structure during formation. In one embodiment, a silicon substrate is exposed to oxygen in the presence of fluorine so that a silicon oxide isolation region is formed. The fluorine reduces the viscosity of the silicon oxide isolation region during formation which results in less lateral, bird&#39;s beak encroachment under adjacent masking stacks and also results in lower internal stress in the isolation region during formation. The lower internal stress and the lessened lateral encroachment result in thicker and improved isolation regions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention generally relates to semiconductor integrated device design and fabrication and, more particularly, to techniques for isolating active areas of integrated circuits.

2. Description of the Related Art

As semiconductor integrated circuit technology advances to Ultra Large Scale Integration (ULSI) technologies, the devices on wafers shrink to sub-micron dimensions and the circuit density increases to several million devices per chip. Since the devices are closer together, isolation of the devices from each other becomes more problematic and more difficult to achieve. As such, the manufacturability and reliability of these devices are of great importance to the semiconductor industry and have received increasing attention recently.

For a given chip size, an increase in the number of active circuit components requires that they be placed in close proximity to each other, thus forcing a corresponding reduction in the surface area of the circuit that can be occupied by electrical isolation structures. The trend for reducing the chip surface area consumed by electrical isolation structures, while maintaining the necessary electrical isolation of adjacent active components, has led to the development of several different isolation techniques.

The most common isolation fabrication technique is a process known as LOCOS (for LOCalized Oxidation of Silicon). In the LOCOS process, the substrate is oxidized to form an isolation structure over the selected regions. These oxidized regions are known as field oxide regions and they are typically positioned so as to separate active areas on the wafer where devices, such as transistors, will subsequently be formed.

In the conventional LOCOS technique, the process typically begins with the growth of a thin pad oxide layer over the wafer surface. The function of this layer is to prevent transfer of stresses between the silicon substrate and the subsequently deposited layers. Following this, a layer of silicon nitride mask is deposited on top of the pad oxide layer and lithographically defined to retain the nitride over the active device regions of the wafer. The nitride layer is etched from the area between the active device areas where the field oxide (silicon dioxide) isolation structure is to be thermally grown.

Although the LOCOS process offers high reliability and proven high volume manufacturing compatibility, the effectiveness of this technique is limited by two important factors. One factor is active area loss due to lateral encroachment of the growing field oxide, often referred to as "bird's beak" encroachment, and the other factor is the problem of the field oxide isolation region thinning during formation which occurs especially in the narrow fields during the field oxide growth stage.

These problems are illustrated in FIG. 1, which shows a cross-section of a portion of a silicon substrate 40 having field oxide isolation regions 50a and 50b formed between a plurality of nitride masking stacks 60. The masking stacks 60 are positioned over the active areas 70 of the wafer 40. The lateral oxide encroachment into the active area is denoted by the distance labeled "W", and the field oxide thicknesses for the narrow and the wide regions are denoted as "t^(n) _(ox) " and "t^(w) _(ox) " in isolation structures 50a and 50b, respectively. The bird's beak encroachment is the result of lateral diffusion of the oxidants at the edges of the nitride masking stack and this bird's beak encroachment causes the oxide layer to grow under and lift the edges of the nitride masking stack.

Although the length of the lateral encroachment depends upon a number of parameters, including the thickness of the pad oxide, nitride and isolation oxide layers, as well as the oxidation temperature and pressure, the encroachment is generally related to the balance between the stress on the wafer from the masking stack, which inhibits the encroachment, and the stress generated by the growth of the field oxide which encourages encroachment. Both of these stresses introduce an increased number of stress induced defects into the silicon substrate adjacent to the active area, thereby increasing the junction leakage current of devices formed in these areas and, as such, reducing the overall reliability of the device.

Another limitation of LOCOS isolation technologies for submicron structures is the phenomenon of the field oxide thinning effect. Typically, narrower field oxide isolation regions formed on the substrate are thinner than wider field oxide isolation regions. This is illustrated in FIG. 1 wherein the wider isolation region 50b on the right hand side is thicker than the narrower isolation region 50a on the left hand side (T_(ox) ^(n) <T_(ox) ^(w)). This inconsistent thickness of the field oxide isolation regions may also be associated with the build up of stress in the silicon substrate which can reduce the oxidation rate and hence the final oxide thickness.

Furthermore, for a given masking stack thickness on a wafer, the stress generated during the field oxide growth is observed to be a function of the field width. In fact, it is believed that the stress created by the field oxide growing in narrower spacings is sufficient to reduce the diffusivity of the oxidant through the oxide thereby reducing the thickness of the isolation regions. As a result of the field oxide thinning effect, device isolation characteristics in narrow isolation regions can be substantially reduced which can result in unwanted conductivity between the devices formed in adjacent active areas.

This problem has led to techniques for reducing the stress during the growth of the field oxide. For example, it is known that the stress exerted by the growing field oxide can be controlled by varying the viscosity of the field oxide. In particular, reducing the viscosity of the growing field oxide allows oxide to flow better. Methods of reducing the viscosity of the field oxide include employing either a high temperature oxidation process or a high pressure oxidation process (HiPOX). In semiconductor technology, a high temperature oxidation process can be either wet or dry oxidation carried out at a temperature of approximately 1000° C. High temperature oxidation generally reduces the thinning problem in narrow field oxidation regions. This is due to a decrease in field oxide viscosity, which results in an increased oxide flow and a decreased level of stress in the field oxide allowing greater oxide growth. Unfortunately, raising the growth temperature is not a reasonable solution to the bird's beak problem as higher temperatures severely increase bird's beak oxide encroachment under the nitride masking stack. Since both minimal isolation region thinning and lateral oxide encroachment are essential for a high quality and defect free isolation process, there is a need for a better process to provide required viscosity reduction.

In this respect, the HiPOx (for High Pressure Oxidation) process may comprise an improvement. In fact, the HiPOx process reduces the field oxide thinning effect and also reduces the length of bird's beak since the oxidation can be performed at a lower temperature range and in a shorter time period under the high pressure. A HiPOx process is typically carried out at a temperature range of 900-1000° C. and under a pressure range of 20-25 Atm. The oxidation process takes place in a high pressure furnace by using an O₂ gas ambient (dry oxidation) or a steam of H₂ O (wet oxidation) as oxidants.

However, even though the HiPOx process provides some advantages over other field oxide growth techniques, problems with the process and the special high pressure equipment have limited its acceptance in the industry. In particular, there are significant safety problems associated with high pressure oxidation due to the high pressure gasses that are used during the process. To address these safety problems, and also to accomplish the process, expensive and large high pressure furnaces and related equipment must be used to perform the process.

As is apparent, there is a need in current semiconductor technology for improved methods of forming isolation regions to reduce lateral encroachment and thinning of the isolation structures, thereby permitting smaller isolation structures to be used. To this end, there is a need to reduce the viscosity of the oxide during the field oxidation isolation process thereby reducing the stress during the oxidation processes. Further, there is a particular need for a technique for forming isolation regions whereby the viscosity is lowered, without using special equipment and the resulting thickness is highly uniform.

SUMMARY OF THE INVENTION

The aforementioned needs are satisfied by the process of the present invention which comprises exposing regions of a semiconductor wafer to an isolation structure forming agent and a viscosity reducing agent. The isolation structure forming agent changes regions of the semiconductor wafer into isolation structures and the viscosity agent decreases the viscosity of the isolation structures during formation. As a result of the decrease in viscosity, lateral encroachment of the isolation structures into adjacent active areas is reduced. Additionally, the decrease in the viscosity is accompanied by a decrease in the internal stress in the isolation structure during formation which enhances diffusion of the isolation structure forming agent to the semiconductor substrate, thereby resulting in thicker isolation structures.

In the preferred embodiment, a semiconductor wafer is masked and then regions of the wafer are exposed. An oxidation step is then performed whereby the semiconductor wafer is oxidized to form the isolation structure. During at least some of the time that the oxidation step is performed, a doping agent that reduces the viscosity of the oxidized semiconductor agent is added to the oxidation step. In one particular implementation, a silicon wafer is oxidized in the presence of fluorine which results in a silicon oxide isolation structure that has a decreased viscosity during formation.

The decrease in viscosity results in a decrease in the forces that prompt volumetric expansion of the isolation structure. This inhibits volumetric expansion underneath masking stacks as the masking stacks exert a compressive force on the portion of the silicon substrate underneath the masking stack. Hence, there is less lateral encroachment, i.e., bird's beak encroachment, of the silicon oxide isolation structure into the regions under the masking stacks that can comprise the locations of active areas of the wafers.

Further, the decrease in viscosity of the silicon oxide results in oxygen molecules more readily diffusing through the silicon oxide isolation structure under formation to the interface between the silicon substrate and the silicon oxide isolation structure. This results in thicker silicon oxide isolation structures and is particularly useful in applications requiring very narrow isolation structures.

These and other objects and advantages of the present invention will become more fully apparent from the following description taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a silicon wafer portion of the prior-art having a patterned nitride mask and field oxide isolation regions grown on the top surface;

FIG. 2A is a cross-sectional view of a silicon wafer portion having a pad oxide layer grown on the top side;

FIG. 2B is a cross-sectional view of the wafer shown in FIG. 2A wherein a layer of silicon nitride has been deposited on the top of the pad oxide layer;

FIG. 2C is a cross-sectional view of the wafer shown in FIG. 2B wherein the nitride masking stack has been patterned and etched to expose regions of the substrate where isolation structures are to be formed;

FIG. 2D is a cross-sectional view of the wafer shown in FIG. 2C wherein field oxide isolation structures are formed in the substrate using the method of the preferred embodiment; and

FIG. 3 is a detailed cross-sectional view of the wafer shown in FIG. 2D wherein the stresses and forces occurring during the growth of the isolation region of the preferred embodiment are schematically illustrated.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Reference will now be made to the drawings wherein like numerals refer to like parts throughout. FIG. 2A illustrates that a buffer layer 102 is initially grown on a silicon substrate 100. Specifically, in the preferred embodiment, the buffer layer 102 is comprised of a thin layer of silicon dioxide (SiO₂) of about 20-300 Å thick that is grown on a clean surface of the silicon wafer 100. This SiO₂ layer is generally known as pad oxide layer 102 and provides a stress-relief buffer between the silicon surface and an overlying layer of masking material.

It will be understood that the semiconductor "substrate," as used herein, refers to a semiconductor layers or structure which includes active areas (e.g., transistor source/drains) of semiconductor devices. For instance, the substrate may comprise a monocrystalline silicon wafer, or a silicon structure over an insulating layer for integrated circuits employing silicon-on-insulator (SOI) technology.

FIG. 2B illustrates that, subsequent to the growth of the pad oxide layer 102, a layer of masking material 104 is formed on the pad oxide layer 102. In the preferred embodiment, the layer of masking material 104 is comprised of a layer of silicon nitride that is about 2000 Å thick. As is understood in the art, the silicon nitride layer 104 is essentially an oxidation masking material which is used during the formation of field oxide isolation regions on the substrate 100. The silicon nitride layer 104 is typically deposited by a chemical vapor deposition (CVD) of dichlorosilane (SiH₂ Cl₂) and ammonia (NH₃) at temperatures between about 600° C. and 800° C., according to the overall reaction:

    3SiH.sub.2 Cl.sub.2 +4NH.sub.3 →Si.sub.3 N.sub.4 +6HCl+6H.sub.2

As shown in FIG. 2C, the process is followed by the patterning of the masking layer 104 with a photoresist pattern and etching through the masking material 104 to expose and define a plurality of regions 106 on the silicon substrate 100 where isolation structures are to be formed. As shown in FIG. 2C, the patterning and etching of portions of the masking material 104 also results in the formation of a plurality of masking stacks 110, comprised of portions of the layer of masking material 104 and the layer of buffer material 102, on the first surface of the substrate 100.

As will be described below, the thickness and the mechanical properties of the masking stack 110 influence the quality of the isolation structures formed in the regions 106. In general, a thicker mask stack 110 allows less bird's beak oxide encroachment during the field oxide growth, since a thicker masking layer is stiffer and resists the edge lifting that accompanies bird's beak penetration. However, if the nitride layer is too thick, it is likely to crack. In the preferred embodiment, the thickness of the masking stack 110 is optimized between about 1500 Å and 2500 Å.

As illustrated in FIG. 2D, after the formation of the nitride mask 110, a plurality of field oxide isolation regions 112 are then thermally grown at the exposed regions 106 of the silicon substrate 100. As is understood, the field oxide regions 112 can be grown by means of either wet oxidation (water steam) or dry oxidation (O₂ gas) according to the general formulas:

    Si(solid)+2H.sub.2 O(water steam)→SiO.sub.2 +2H.sub.2

    Si(solid)+O.sub.2 (gas)→SiO.sub.2

In the preferred embodiment of the invention, the field oxide growth is carried out by means of atmospheric pressure wet oxidation at a temperature range of approximately 1000° C. and to a thickness of approximately 2000 Å. However, as a departure from the prior art oxidation techniques, a viscosity reducing agent or dopant is also introduced into the wet oxidation ambient so as to apply viscosity reducing dopant atoms, schematically represented in FIG. 2D by reference number 114, to the growing field oxide regions 112.

Preferably, the dopant is fluorine which can be introduced into oxidation ambient by a variety of fluorine containing gases such as NF₃, CF₄, SF₆, C₂ F₆ or SiF₄. The final field oxide regions 112 of the preferred embodiment contain approximately 1% by weight of fluorine dopant and the amount of fluorine dopant incorporation into the field oxide is controlled by the flow rate of the fluorine containing gas during the field oxide oxidation. As an example, in the present invention, preferably, a NF₃ gas with 5-25 sccm flow rate at 900-1150° C. is used. In accordance with the principles of the present invention, the deliberate introduction of a viscosity reducing agent, such as a fluorine species, into the oxidation ambient causes a reduction in the viscosity of the growing field oxide.

FIG. 3 illustrates the effects of the introduction of the viscosity reducing agent during the formation of the isolation region 112 in greater detail. Specifically, FIG. 3 illustrates that the masking stack 110 exerts a force, represented by the arrows 120, that is generally directed downward and is generally compressive against the substrate 100. Furthermore, during the growth of the field oxide isolation regions 112, the volumetric expansion of the field oxide isolation region 112 exerts a force in the direction of the arrows 122 inward and under the masking stack 110. Typically, there is a portion 130 of the field oxide isolation region 112 (the Bird's beak) that laterally encroaches underneath the masking stack 110 during the field oxidation step.

It will be appreciated that at an equilibrium point, the downward force 120 will be balanced by the inward force 122 thereby limiting the size of the Bird's beak portion 130 encroaching under the masking stack 110. Furthermore, during the formation step, the material that is transforming the substrate 100 into the isolation region 112 preferably diffuses through the isolation region 112 after the initial reaction and transforms individual atoms of the substrate into the material of the isolation region, i.e., transforms the silicon substrate 100 into a silicon oxide in the preferred embodiment. The viscosity reducing agent has the tendency to reduce the overall viscosity of the material forming the isolation region 112 while the region 112 is under volumetric expansion.

Hence, in the preferred embodiment, the inward force 122 exerted on the substrate 100 as a result of the volumetric expansion of the isolation region 112 is lowered. This results in the bird's beak portion 130 of the region 112 being reduced and, since there has been a reduction in the overall amount of stress on the semiconductor substrate 100, fewer stress induced defects are formed in the substrate 100.

Furthermore, it will be appreciated that if the growth of the field oxide isolation region 112 into the substrate 100 positioned under the masking stack 110 is limited, then additional growth of the field oxide isolation region 112 will have a greater tendency to occur towards the center 118 of the isolation region thereby reducing the problem of thinning isolation regions. In other words, if the force 122 of expansion underneath the masking stacks 110 is lowered as a result of the decrease in the viscosity of the material forming the isolation region, then the compressive force 120 will have the tendency to increase the thickness of the field oxide region 112 as represented by the arrow 140.

In the preferred embodiment, the formation of the isolation regions 112 occurs as a result of the oxygen molecules diffusing into the substrate 100 and bonding with a silicon atom to form silicon oxide. The addition of the fluorine results in some of the fluorine atoms bonding with the silicon atoms in the substrate 100. It will be appreciated that, as the isolation region 112 grows, the oxygen molecules will have to diffuse through the isolation region 112 to reach the silicon substrate 100. This diffusion is hampered, in the prior art, by internal stresses in the growing isolation region 112 which contributes to the thinning of the isolation region 112.

By adding the viscosity reducing agent 114, e.g., fluorine in the preferred embodiment, the stress within the isolation region 112 during growth is lowered which allows for more diffusion of oxygen molecules to the silicon substrate 100. Consequently, the addition of the viscosity reducing agent in the preferred embodiment results in thicker field oxide isolation regions 112 as the oxygen molecules can more readily diffuse through the center of the isolation region 112.

It will be appreciated that the stress build up in the isolation region 112 is more pronounced in narrower isolation regions, i.e., regions that occupy smaller surface areas of the semiconductor substrate. Hence, lowering the viscosity by the addition of the viscosity reducing agent allows for smaller dimensioned isolation structures while minimizing both the problems of field oxide thinning and lateral, bird's beak, encroachment. In addition, the process of the preferred embodiment can be performed using equipment and techniques of the prior art and does not require the addition of expensive high pressure equipment to perform the process.

Hence, it will be understood that fluorine doping reduces the viscosity of the field oxide during growth of the field oxide isolation regions 112 and allows the field oxide to grow in thickness rather than grow laterally. Clearly, the masking stack 110 becomes significantly more effective against the penetrating bird's beak if the viscosity of the field oxide is lowered, thereby reducing the encroaching force 122. Thus, due to the lower viscosity of the field oxide, nitride masking stack edges are more resistant to lifting caused by the penetrating bird's beak region 130. As a result, a shorter bird's beak oxide encroachment is also achieved.

It would be understood that the improved LOCOS technique provided by this embodiment discloses a method for reducing the viscosity of the growing field oxide by means of adding a fluorine containing gas into the oxidation ambient. The presence of fluorine in the forming field oxide lowers the viscosity and allows it to flow more readily at conventional processing temperatures (1000° C.), thereby reducing the internal stress of the growing field oxide. Furthermore, in connection with the viscosity, reducing the internal stress results in shorter bird's beak oxide encroachment and less oxide thinning. Additionally, the fluorine incorporated oxidation step of the process eliminates the use of expensive high pressure or high temperature oxidation processes to decrease viscosity of the growing field oxide. Therefore, the process is inexpensive and efficient.

Hence, although the foregoing description of the preferred embodiment of the present invention has shown, described and pointed out the fundamental novel features of the invention, it will be understood that various omissions, substitutions, and changes in the form of the detail of the apparatus as illustrated as well as the uses thereof, may be made by those skilled in the art, without departing from the spirit of the present invention. Consequently, the scope of the present invention should not be limited to foregoing discussions, but should be defined by the appended claims. 

What is claimed is:
 1. A method of forming an isolation structure in a semiconductor substrate comprising:positioning a layer of masking material over a first surface of said substrate; selectively etching said layer of masking material to expose a region of said first surface and to define a masking stack comprising said masking material positioned on said first surface; and forming an isolation structure in said exposed region by exposing said region to an isolation structure forming agent and a viscosity reducing agent, wherein said isolation structure incorporates about 1% by weight of said viscosity reducing agent.
 2. The method of claim 1, wherein positioning said layer of masking material over said first surface of said substrate comprises positioning a layer of silicon nitride over said first surface.
 3. The method of claim 1, wherein forming said isolation structure comprises exposing said region of said substrate to an oxygen laden gas to produce a silicon oxide isolation region.
 4. The method of claim 3, wherein exposing said region of said substrate to said oxygen laden gas comprises exposing said region to an oxygen and fluorine laden gas.
 5. The method of claim 4, wherein exposing said region to said oxygen and fluorine laden gas comprises performing a wet oxidation process on said substrate in the presence of fluorine.
 6. The method of claim 1, wherein said forming step comprises diffusing said forming agent and said viscosity reducing agent into said substrate and combining said forming agent with atoms of said substrate.
 7. The method of claim 6, wherein said forming step comprises reducing a volumetric expansion of said isolation region into a portion of said substrate of said wafer positioned under said masking stack, relative to a volumetric expansion from forming an isolation structure absent said viscosity reducing agent.
 8. The method of claim 7, wherein said forming step comprises inhibiting build up of stress within said isolation structure and allowing greater diffusion of said isolation structure forming agent through a forming isolation structure to the atoms forming said substrate of said wafer.
 9. The method of claim 8, wherein said forming step comprises increasing a thickness of said isolation structure, relative to a thickness from an isolation structure formed without said viscosity reducing agent.
 10. A method of forming an isolation structure in a semiconductor substrate of a semiconductor comprising:exposing to an ambient environment a region of said semiconductor substrate on a first surface of said substrate; defining a masking stack positioned on said first surface adjacent said region; exposing said region to a transforming agent, whereby said transforming agent diffuses into said substrate and transforms said substrate into said isolation structure; and exposing said region to a viscosity reducing agent, during said step of exposing said region to said transforming agent, wherein said isolation structure incorporates about 1% by weight of said viscosity reducing agent.
 11. The method of claim 10, wherein defining said masking stack comprises positioning a layer of masking material over said first surface of said semiconductor substrate and etching said masking material to expose said region of said first surface to said ambient environment.
 12. The method of claim 11, wherein said step of exposing said region to said transforming agent comprises exposing said region to a wet oxidation process.
 13. The method of claim 12, wherein said step of exposing said region to said viscosity reducing agent comprises exposing said region to a fluorine gas while simultaneously exposing said agent to said wet oxidation process.
 14. The method of claim 13, wherein said reduced viscosity of said isolation structure during formation results in reduced encroachment of said isolation structure into a portion of said substrate positioned underneath said masking stack.
 15. The method of claim 14, wherein said reduced volumetric expansion of said isolation region into said portion of said substrate positioned under said masking stack, in combination with said reduced stress in said isolation structure during formation, results in said isolation structure having a greater thickness.
 16. A method of forming a silicon oxide isolation structure in a silicon wafer having a substrate comprised of silicon atoms, comprising:positioning a layer of masking material over a first surface of said wafer; selectively etching said layer of masking material to expose a region of said first surface of said wafer and to define a masking stack comprising said masking material positioned on said first surface of said wafer; growing a silicon oxide isolation region in said region of said silicon wafer by exposing said region to oxygen wherein said oxygen diffuses into said silicon wafer and combines with said silicon atoms of said substrate to form said silicon oxide isolation region; and exposing said region to a viscosity reducing agent during said step of growing said silicon oxide isolation region, wherein said silicon oxide isolation region comprises about 1% by weight of said viscosity reducing agent.
 17. The method of claim 16, wherein said nitride masking stack exerts a compressive force against said a portion of said substrate of said silicon wafer and wherein lateral encroachment of said silicon oxide isolation structure, during growth of said silicon oxide isolation structure, into said portion of said substrate is reduced as a result of both said compressive force and said reduced viscosity of said silicon oxide isolation structure.
 18. The method of claim 17, wherein said reduced viscosity of said isolation structure during formation results in reduced internal stress in said isolation structure during formation.
 19. The method of claim 18, wherein said reduced volumetric expansion of said isolation region into said portion of said substrate positioned under said masking stack, in combination with said reduced stress in said isolation structure during formation, results in said isolation structure having a greater thickness.
 20. The method of claim 19, wherein said step of exposing said region to said viscosity reducing agent comprises exposing said region to fluorine.
 21. The method of claim 20, wherein said step of exposing said region to said viscosity reducing agent comprises exposing said region to a gas containing oxygen and fluorine.
 22. A method of forming an isolation region in a substrate of a wafer comprising:oxidizing a portion of said substrate of said wafer; and exposing said portion of said substrate to an agent for reducing the viscosity of said exposed portion, wherein said agent forms about 1% by weight of said isolation region.
 23. The method of claim 22, further comprising the steps of:positioning a layer of masking material over a first surface of said wafer; and selectively etching said layer of masking material to expose said portion of said substrate.
 24. The method of claim 22, wherein the step of oxidizing said portion of said substrate comprises exposing said substrate to a wet oxidation process.
 25. The method of claim 24, wherein the step of exposing said portion of said substrate to said viscosity reducing agent comprises exposing said region to a fluorine laden gas while simultaneously exposing said portion to said wet oxidation process. 